Dyeing human hair with n-arylsulfon-amides and aromatic amines

ABSTRACT

IN AN AQUEOUS COMPOSITION FOR DYEING HUMAN HAIR COMPRISING AN OXIDATION DYESTUFFS COMBINATION OF A DEVELOPER COMPONENT AND A COUPLING COMPONENT AND CUSTOMARY DYESTUFF ADJUVANTS, THE IMPROVEMENT WHICH COMPRISES UTILIZING AS SAID OXIDATION DYESTUFF COMBINATION, FROM 0.3% TO 5% BY WEIGHT OF AN OXIDATION DYESTUFF COMBINATION OF (A) A DEVELOPER COMPONENT COMPOUND HAVING THE FORMULA   2-(R-O2S-NH-),4-(R1-N(-R2)-),R3-ANILINE   WHEREIN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROCARBON HAVING FROM 1 TO 10 CARBON ATOMS AND AN OXYGENATED HYDROCARBON HAVING FROM 7 TO 10 CARBON ATOMS, R1 AND R2 ARE ALKYL HAVING FROM 1 TO 4 CARBON ATOMS AND R3 IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING 1 TO 4 CARBON ATOMS AND ALKOXY HAVING FROM 1 TO 4 CARBON ATOMS, AND (B) A COUPLING COMPONENT COMPOUND, KNOW FOR HAIR DYES, HAVING THE FORMULA   X-AR-Y   WHEREIN AR REPRESENTS AN AROMATIC NUCLEUS, X REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, AMINO, KIALKYLAMINO HAVING FROM 1 TO 4 CARBON ATOMS IN THE ALKYLS AND HYDROXYL, AND Y REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF AMINO, DIALKYLAMINO HAVING FROM 1 TO 4 CARON ATOMS IN THE ALKYLS AND HYDROXYL, AS WELL AS THE METHOD OF DYEING HUMAN HAIR UTILIZING SAID OXIDATION DYESTUFF COMBINATION OF A DEVELOPER COMPONENT AND A COUPLING COMPONENT.

United States Patent ()flice 3,695,823 Patented Oct. 3, 1972 3,695,823 DYEING HUMAN HAIR WITH N-ARYLSULFON- AMIDES AND AROMATIC AMINES Rolf Rehberg, Niederhofheim, and Erik Wiskott, Bottmingen, Switzerland, assignors to Therachemie Chemisch Therapeutische Gesellschaft m.b.H., Dusseldorf, Germany No Drawing. Filed Feb. 11, 1970, Ser. No. 10,642

Int. Cl. A61k 7/12 US. Cl. 8-102 4 Claims ABSTRACT OF THE DISCLOSURE wherein R is a member selected from the group consisting of a hydrocarbon having from 1 to carbon atoms and an oxygenated hydrocarbon having from 7 to 10 carbon atoms, R and R are alkyl having from 1 to 4 carbon atoms and R is a member selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms and alkoxy having from 1 to 4 carbon atoms, and (b) a coupling component compound, known for hair dyes, having the formula wherein Ar represents an aromatic nucleus, X represents a member selected from the group consisting of hydrogen, amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls and hydroxyl, and Y represents a member selected from the group consisting of amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls and hydroxyl, as Well as the method of dyeing human hair utilizing said oxidation dyestufi combination of a de-- veloper component and a coupling component.

THE PRIOR ART The use of oxidation dyestuffs for dyeing human hair has been known for many years, phenylenediamines being used in particular as the dyestuff components. Further it has also already been proposed to use diaminopyridines for this purpose. The said compounds are converted into the dyestuffs on the hair by oxidation either with air or, especially, by addition of chemical oxidizing agents such as hydrogen peroxide. These known hair dyes are used to a considerable extent. However, they have the disadvantage, among others, that the dyestuiis formed do not product any uniformly defined compounds and may in some cases give further reaction if a different time of action is employed. They are also diificult to remove.

OBJECTS OF THE INVENTION An object of the present invention is, in an aqueous composition for dyeing human hair comprising an oxidation dyestuffs combination of a developer component and a coupling component and customary dyestuif adjuvants, the improvement which comprises utilizing as said oxidation dyestutf combination, from 0.3% to 5% by weight of an oxidation dyestufi combination of (a) a developer component compound having the formula wherein R is a member selected from the group consisting of a hydrocarbon having from 1 to 10 carbon atoms and an oxygenated hydrocarbon having from 7 to 10 carbon atoms, R, and R are alkyl having from 1 to 4 carbon atoms and R is a member selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms and alkoxy having from 1 to 4 carbon atoms, and (b) a coupling component compound, known for hair dyes, having the formula X-Ar-Y wherein Ar represents an aromatic nucleus, X represents a member selected from the group consisting of hydrogen, amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls and hydroxyl, and Y represents a member selected from the group consisting of amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls and hydroxyl.

Another object of the present invention is, in the process of dyeing human hair which comprises treating the hair at a temperature of from 10 C. to 40 C. with an aqueous composition for dyeing human hair comprising an oxidation dyestutf combination of a developer component and a coupling component and customary dyestuif adjuvants in the presence oof an oxidizing agent, the improvement which comprises utilizing as said oxidation dyestuif combination, from 0.3% to 5% by weight of an oxidation dyestutf combination of (a) a developer component compound having the formula wherein R is a member selected from the group consisting of a hydrocarbon having from 1 to 10 carbon atoms and an oxygenated hydrocarbon having from 7 to 10 carbon atoms, R and R are alkyl having from 1 to 4 carbon atoms and R is a member selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms and alkoxy having from 1 to 4 carbon atoms, and (b) a coupling component compound, known for hair dyes, having the formula X-Ar--Y wherein Ar represents an aromatic nucleus, X represents a member selected from the group consisting of hydrogen, amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls and hydroxyl, and Y represents a member selected from the group consisting of amino, dia1ky1- amino having from 1 to 4 carbon atoms in the alkyl and hydroxyl.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION It has now been found that the drawbacks of the prior art can be largely avoided and the objects of the invention can be achieved if the process described below for dyeing human hair with solutions, emulsions or creams which contain oxidation dyestuffs and the usual additives for hair dyes, is carried out.

The present invention therefore provides an oxidation dyestulf for dyeing human hair comprising from 0.3% to by weight of (a) a developer component which is a compound of the general Formula I NHS 023 1 TH: (I)

in which R represents a hydrocarbon residue, preferably consisting of a hydrocarbon having from 1 to carbon atoms and an oxygenated hydrocarbon having from 7 to 10 carbon atoms, and more particularly consisting of alkyl having from 1 to 8 carbon atoms, cycloalkyl having from 6 to 7 carbon atoms, phenyl, alkylphenyl having from 7 to 10 carbon atoms and alkoxyphenyl having from 7 to 10 carbon atoms; R and R each represents alkyl having from 1 to 4 carbon atoms, preferably methyl and ethyl; and R represents a hydrogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms, preferably methyl and methoxy in the 6 position; and (b) a coupling component known for hair dyes and based on an aromatic compound containing amino and/or hydroxyl groups, preferably a compound having the Formula III in which Ar represents an aromatic nucleus, preferably consisting of naphthylene, hydroxynaphthylene, aminonaphthylene, phenylene, aminophenylene, hydroxyphenylene, toluylene, alkoxyphenylene having from 7 to 10 carbon atoms and quinolylene; X represents hydrogen, amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls or hydroxyl; and Y represents amino, dialkylamino having from 1 to 4 carbon atoms in the alkyls or hydroxyl.

The present invention also provides a process for dyeing hair comprising treating the hair in the presence of an oxidizing agent and at a temperature of from 10 to 40 C. with a substituted N-aryl-sulfonamide of the above general Formula I and a coupling component known or hair dyes and based on an aromatic compound containing amino and/or hydroxyl groups. The alkyl and alkoxy residues in the above compounds may have straight or branched chains and may be the same or different.

The hydrocarbon residue R in Formula I may be present in the form of an aliphatic, aromatic or cycloaliphatic residue. Straight or branched chain alkyl containing 1 to 6 carbon atoms or an aromatic residue are preferably used, and the readily available N-aryl-sulfonamides of the general Formula II in which R and R each represents an alkyl residue containing 1 to 4 carbon atoms, preferably methyl and ethyl, and R represents a hydrogen atom or an alkyl or alkoxy group containing 1 to 4, preferably 1 to 2, carbon atoms, are utilized in particular.

The most readily available substituted N-aryl-sulfonamides include the following:

3-phenylsulfonamino-4-aminodimethylaniline 3-pheny1sulfonamino4-arninodiethylaniline 3-methylsulfonamino-4-aminodimethylaniline 3-methylsulfonamino-4-aminodiethylaniline 3-methylsulfonamino-4-amino--methyldimethylaniline 3-methylsulfonamino-4-amino-6-methyldiethylaniline 3-butylsulfonamino-4-aminodimethylaniline 3-butylsulfonamino-4-aminodiethylaniline 3-hexylsulfonamino-4-aminodimethylaniline 3-hexylsulfonamino-4-aminodiethylaniline 3-ethylsulfonamino-4-amino-G-methoxydimethylaniline 3-cyclohexylsulfonamino-4-aminodiethylaniline 3- 3 '-methoxypheny1sulfonamino) -4-amino dimethylaniline 3-(3'-methoxyphenylsulfonamino)-4-aminodiethylaniline 3-(4'-methylphenylsulfonamino)-4-aminodiethylaniline.

The preparation of the substituted N-aryl-sulfonamides (termed the developer component) of the type mentioned is carried out by known methods. Thus, for example, 3 alkylsulfonamino dialkylaniline or 3 arylsulfonamino-dialkylaniline may be treated with nitrous acid and the nitroso compound formed reduced to the desired amine, or such dialkylanilines may be nitrated and then reduced.

Instead of starting from the substituted N-aryl-sulfonamides which contain an amino group in the alkyl residue, it is often expedient to prepare the corresponding salts organic or inorganic acids, especially hydrochloric aci Suitable coupling components include aromatic amines and diamines, phenols, naphthols and aminophenols. The meta-compounds are preferably used in the case of the diamines, aminophenols and phenols. When diamines are used, those in which the hydrogen atoms of the amino groups are substituted by lower alkyl residues (C -C may also be used.

The following compounds are examples of the said coupling components:

m-phenylenediamine m-aminophenol anisidine 2,4-diaminoanisole m-toluylenediamine resorcinol pyrocatechol resorcinol-monoethyl ether m-aminoresorcinol 1,5-dihydroxynaphthalene 1,6-dihydroxynaphthalene 1,7-dihydroxynaphthalene 2,7-dihydroxynaphthalene 1,5-aminoor 1,8-amino-hydroxynaphthalene a-naphthol 8-hydroxyquinoline 1,8-diaminonaphthalene.

The coupling component is suitably used in approximately a molar amount with respect to the N-arylsulfonamide. It is not generally detrimental, however, if the last-named compound is present to some degree in more or less than the stoichiometric amount. Preferably, the coupling component is present in a mol ratio of 0.8 to 1.3 for each mol of N-arylsulfonamide. Mixtures of the individual dyestuif components may also be used. It is frequently advantageous to use the N-arylsulfonamide in the form of its salt with an inorganic or organic acid, especially the salt of sulfuric acid, oxalic acid and hydrochloric acid.

The dyestulf can be produced, for example, as shown by the following equation, where 3-phenylsulfonamino-4- aminodiethylaniline is the developer component and 1,5- dihydroxynaphthalene is the coupling component:

1120 (02mm NHS 02otHt wit The above equation shows that phenazine dyestuffs are formed and that the type of the hydrocarbon residue R of the general Formula I is immaterial, since it is split off during the formation of the dyestuff. Moreover, the dyestulf formation must take place on the hair itself, since otherwise no useful absorption of dye occurs.

As with other oxidation dyestuffs, the dye can be developed both by oxygen of the air and by chemical oxidizing agents, such as preferably hydrogen peroxide or its addition products, especially with urea, melamine and sodium borate. The dyeing of the hair is effected at a temperature from 10 C. to 40 C., preferably at room temperature. The dye treatment of the living human hair is preferably for a period of 10 minutes to 1 hour followed by a rinsing of the hair.

The hair dyeing compositions may be applied in the form of aqueous solutions, but especially in the form of creams or emulsions. For this purpose, the N-arylsulfonamides and the coupling components are mixed with any optional wetting agents or washing compositions, especially anionic or non-ionic substances. Suitable wetting and washing agents are especially alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid ethanolamides, products of addition of ethylene oxide to fatty acids and fatty alcohols, and fatty alcohol alkyl ether and polyalkyl ether sulfates.

The absorptive capacity of the above-mentioned dyestuffs is also good when they are in admixture with such compositions. Consequently, the hair dyes can be pro duced in the form of shampoos, especially of cream shampoos, which are much desired in practice.

Further, thickeners such as, for example, methylcellulose, star-ch, higher fatty alcohols, Vaseline (petrolatum), parafiin oil and fatty acids, and also perfume or hair conditioning substances such as, for example, pantohenic acid and cholesterol, may be admixed with the compositions of the invention.

The added substances are used in the amount customary for these purposes. Suitable added amounts of wetting agents are, especially, 0.5% to 30% by weight, and of thickeners, are 0.1% to 25% by weight, referred in each case to the total composition. The concentration of the dyestulf components (developer and coupling components) is to a certain extent dependent on the purpose of use and amounts, in each case, to 0.3% to 5% by weight, preferably 0.5;% to 2.5% by weight. These quantities are also with reference to the total composition.

The hair dyes are adjusted so that they are alkaline, preferably to a pH value of 8 to 10. The dyeings obtained with the hair dyes described above have good properties with respect to light, washing and rubbing, and, in contrast to the usual compositions based on oxidation dyestuffs, the dyeings can easily be removed with reducing agents such as sodium hydroxymethanesulfinate.

The present invention will be further described by Way of reference to the following specific examples. These, however, are not to be deemed limitative of the practice of the invention.

EXAMPLE 1- 2 parts by weight of 3-phenylsulfonamino-4-aminodiethylaniline dihydrochloride and 1 part by weight of 1,5- dihydroxynaphthalene were dissolved in water. 50 parts by weight of an emulsion formed from 10 parts by weight of a fatty alcohol (hydrocarbon chain length G -C 26 parts by weight of sodium lauryl ether sulfate and 64 parts by weight of water were added. The pH was adjusted to 9.5 and the solution was then treated with 1 part by weight of hydrogen peroxide and made up to parts by weight with water.

The dye cream so obtained dyed gray hair brown when treated at 25 C. during a period of 30 minutes. After the dye treatment, the hair was rinsed with water and shampooed.

EXAMPLE 2 EXAMPLE 3 Dye creams were prepared as. described in Example 1,

but the compounds indicated in the following Tables 1 and 2 were used as the substituted N-arylsulfonamides (developer component) and coupling component. Under analogous conditions and with a period of action of about 25 minutes and a temperature of 35 C., the dye colors indicated in the right-hand columns of the tables were obtained.

The same results were obtained when the substituted N-arylsulfonamides given as the developer component were used in the form of the corresponding salts with oxalic acid, maleic acid, sulfuric acid or hydrochloric acid.

TABLE 1 Coupling No. N-arylsulfonamlde component Dye color 1 3-phenylsulfonamlno-4- Pyrocateehol-.-- Gray-brown.

amino-diethylaniline. 2 -.do 1,8maphthyl- Black-brown.

enediamine. 3 .-do oe-Naphtho1. Red-brown. 4 3'methylSUlf0namin0-4- 1,5-dihydroxy- Brown.

amino-G-methyl-diethylnaphthalene. aniline. 5 -.do Pyrocatechol Copper-brown. 6 -.do 1,5-diaminorown.

naphthalene. 7 ...do 2,4-diamlno- Dark green.

anisole. 8 3-methylsulfonamino4- 1,5-dihydroxy- Brown-red.

amino-diethylani1ine. naphthalene. 9 ..do Pyrocatechol Violet-brown. 10 ..do 1,8-na1qhthyl- Gray-brown.

enediamine. 11 -.do 2,4-diamino- Gray-green.

anisole. 12 -.do m-Toluylene- Brown-green.

iamine.

TABLE 2 Coupling No. N-arylsulfonamide component Dye color 1 3-methylsu1ionamino4- 1,5-d1hydroxy- Brown.

amino-fi-methyl-dinaphthalene. methylaniline. 2 do 1,5dlarnino- Do.

naphthalene. 3 do PyrocatechoL... Copper-brown. 4 -.do 2,4-diamino- Dark green.

anlsole. 5 3-phenylsulionamino-4- 1,8-naphthyl- Black-brown.

aminodimethylanillne. enediamine. 6 -.do a-Naphthol Red-brown. 7 ..do Pyrocatechol Gray-brown. 8 3-methylsulfonamino-4- 2,4-dlarnino- Gray-green.

amino-dimethylanillne. anlsole. 9 do m-Toluylene- Brown-green.

diamine. 10.- do Pyromrer-hnl Violet-brown. 11 do 1,8-naphthyl- Gray-brown.

enediam e. 12 do 1,5-dihydroxy- Brown-red.

naphthalene.

The color of the hair dyed as indicated in the above examples could be completely removed again by a 20- minute treatment of the dyed hair with a 3% aqueous Rongalit C (trademark for sodium hydroxymethanesulfinate) solution.

In this example the various N-arylsulfonamides and coupling components were employed in amounts of 2 parts by Weight of N-arylsulfonamide to 1 part by weight of coupling component. However, other ratios such as 0.8 to 1.2 parts by weight of the coupling component can be employed with comparable results.

When dyeing human hair, the hydrogen peroxide should preferably be added to the dye cream just prior to its application to the hair. The time required for dyeing the hair can be widely varied from the times indicated as side reactions causing color changes do not readily occur with the oxidation reaction of the N-arylsulfonamides and coupling components.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood however that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. In the process of dyeing human hair which comprises treating the hair at a temperature of from C. to 40 C. with an effective amount of an aqueous composition for dyeing human hair comprising an oxidation dyestufi combination of a developer component and a coupling component in the presence of an oxidizing agent, the improvement which consists essentially of utilizing as said oxidation dyestuff combination, from 0.3% to 5% by weight of an oxidation dyestufi combination having substantially equimolar amounts of a developer component and a coupling component of (a) a developer component compound having the formula wherein R is a member selected from the group consisting of a hydrocarbon having from 1 to 10 carbon atoms and alkoxyphenyl having from 7 to 10 carbon atoms, R and R are alkyl having from 1 to 4 carbon atoms and R is a member selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms and alkoxy having from 1 to 4 carbon atoms, and (b) a coupling component compound having the formula wherein Ar represents an aromatic nucleus, X represents a member selected from the group consisting of hydrogen, amino, and hydroxyl, and Y represents a member selected from the group consisting of amino and hydroxyl.

2. The process of claim 1 wherein said developer component is present in the form of a salt with an acid selected from the group consisting of organic and inorganic acids.

3. The process of claim 2 wherein said developer component is present in the form of its salt with hydrochloric acid.

4. The process of claim 1 wherein said developer component has the formula wherein R and R have the definitions as set forth in claim 6 and R represents a member selected from the group consisting of hydrogen, alkyl having from 1 to 4 carbon atoms and alkoxy having from 1 to 4 carbon atoms.

References Cited UNITED STATES PATENTS 2,271,238 1/ 1942 -"Vittum et al. 96-100 X 2,414,491 1/ 1947 Tulagin 260556 X 2,543,338 2/1051 Schmidt et al 96-100 X 2,906,587 9/1959 Lantz et a1. 811 X 3,245,795 4/1966 Gaspar 96100 X ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R. 8-11 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,695,823 Dated October 3. 1972 Inventor) I I Rolf Rehberg et a1.

It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

On the cover-sheet insert! [30] Foreign Application Priority Data I Feb. 14;"1969 Germany P 19 07 322 .4

Signed'and sealed this 14th day of January 1975.

(SEAL) 3 Attest:

MCCOY M. GIBSON JR. Attesting Officer C. MARSHALL DANN Commissioner of Patents FORM po'wso USCOMM-DC scan-poo I 5. GOVERNMENT PRINTING OFFICE I UNITED STATES PATENT OFFICE I CERTIFICATE OF CORRECTION Patent 3,695,825 I Dated October 5, 1972 I mfl ROLF REHBERG AND ERIK WISKOTT It is certified that error appears in the above-identified patent and that said Letters. Batentuare xebszwcorzgc 2d. asfihPW P Pafihi Agglication Col; Zine Page L ne Errors 1 4 oflthe I I Insert --Germany-.- after Heading I I "Niederhofheim".

1 '66 I 2 11 Change "product" to "produce".

2 39 3 I 22 Correct the spelling of word "of".

2 71, u 15 I Chahge "alkyl to --a1ky1s--. 5 63 I 10 23 Correct the: spelling of I I I r o -pantoj hen1c claim A 5 Change "claim 6" to --olaim 1 Cited The da te of Schmidt et a1 should I References 3 A be 2/1251.

Signed and sealed this 19th day of November 1974.

(SEAL) I Attest:

MCCOY M. mBoN J RLj I c. MARSHALL DANN L Attes'ting Officer Commissioner of Patents FORM PO-1050 (10-69) USCOMM-Dt'. 60376-P69 u,sv GOVERNMENT PRINTING OFFICE 1!" osu-n4. 

